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SCIENTIA SINICA Chimica, Volume 49, Issue 4: 607-612(2019) https://doi.org/10.1360/N032018-00167

A zirconium-based and amine-functionalized metal-organic framework material for adsorption and controlled release of fragrance

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  • ReceivedJun 12, 2018
  • AcceptedJul 26, 2018
  • PublishedNov 27, 2018

Abstract

In this paper, we studied the adsorption and release behavior of various fragrant molecules to zirconium-based and amine-functionalized metal-organic framework materials (MOF) UiO-66-NH2. The results showed that UiO-66-NH2 has almost no difference in the adsorption of non-polar terpenoid fragrances, but there is significant difference in the adsorption of polar ester fragrance. The fragrance-adsorbed UiO-66-NH2 was characterized by SEM, PXRD and FTIR. No structural collapse and crystal form change was found after the adsorption of fragrant molecules. Amine groups in UiO-66-NH2 can form hydrogen bonds with different ester fragrance, which favor the adsorption and sustain release of fragrance. These MOF materials showed much higher adsorption capacity to fragrant molecules than the traditional adsorbent activated carbon. The release kinetics of ester fragrance was studied by headspace-gas chromatography. It was found the release kinetics was consistent with the Korsmeyer-Peppas model and the pore diffusion was the rate-limiting state of its release.


Funded by

国家重点研发计划纳米科技重点专项(2016YFA0200300)


Acknowledgment

感谢新加坡国立大学赵丹教授提供MOF材料UiO-66-NH2.


Supplement

补充材料

本文的补充材料见网络版http://chemcn.scichina.com. 补充材料为作者提供的原始数据, 作者对其学术质量和内容负责.


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  • Figure 1

    X-ray diffraction patterns of UiO-66-NH2 and UiO-66-NH2@EP (color online).

  • Figure 2

    SEM image (a) and TEM image (c) of UiO-66-NH2. SEM image (b) and TEM image (d) of UiO-66-NH2@EP.

  • Figure 3

    Infrared spectra of EP, UiO-66-NH2 and UiO-66-NH2@EP.

  • Figure 4

    Release curves of pure EP, UiO-66-NH2@EP and UiO-66-NH2@BA (color online).

  • Figure 5

    Korsmeyer-Peppas equation for the release of UiO-66-NH2@EP and UiO-66-NH2@BA (color online).

  • Table 1   Adsorption of ester fragrance by MOF material UiO-66-NH

    MOF

    香料吸附量 (cm3 (STP) g−1) (g (FG) g−1)

    丁酸异戊酯

    己酸乙酯

    2-甲基丁酸乙酯

    乙酸丁酯

    丙酸乙酯

    UiO-66-NH2

    16.1

    (0.114)

    38.1

    (0.246)

    145

    (0.847)

    165.5

    (0.85)

    547

    (2.49)

  • Table 2   Comparison of adsorption of activated carbon and UiO-66-NH on esters

    多孔材料

    总比表面积 (m2 g−1)

    总孔容 (cm3 g−1)

    吸附量 (cm3 (STP) g−1)

    2-甲基丁酸乙酯

    乙酸丁酯

    丙酸乙酯

    活性炭

    886

    0.452

    66.69

    86.25

    444.8

    UiO-66-NH2

    1000

    0.510

    203

    180.28

    587.9

  • Table 3   Release kinetics equations for UiO-66-NH@EP and UiO-66-NH@BA

    UiO-66-NH2@EP

    UiO-66-NH2@BA

    拟合系数R2

    拟合系数R2

    零级释放

    0.846

    0.859

    一级释放

    0.971

    0.962

    Higuchi 释放

    0.981

    0.970

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